Nitro-substituted lactams



ted States Patent NERO-SUBSTITUTED LACTAMS Karl Klager, Monrovia, Calif,assigner t6 Aerojetgeneral Corporation, Aziisa, Caiifi, a corporation ofbio No Drawing. Application July 11, 1955 Serial No. 521,371

17 Claims. c1. see-239.3

This" invention relates to new compositions" of matter and a method fortheir pre aration; In particular, this invention relates to nitrc-substituted lactams having the general formula:

, tals.

in assignees copending application Serial No. 422,649,

filed April 12, 1954, now abandoned, as well as nitrocellulose. Thepolyurethane propellants are solid, smokeless, self-sustaining rocketpropellants. In usev they are enclosed ina conventional rocket chamberhaving an opening or exit nozzle at one end. The propellant can be igv 1nited by means of a conventional igniter such as an electric squib-blackpowder igniter whereby combustionof the propellant grain is initiated.The gases produced by this combustion are expelled through the exitnozzle thereby imparting propulsive force to the rocket motor.Commercial plasticizers used at the present time are noneXplosive andhence detract from the explosive; or pro'pellant power of thenitropolymersinto which they are incorporated. The compounds of thisinvention, however, are not only plasticizers but alsotexhibit highexplo'sive energy.

The nitropolymers can be polymerized inathe presence of th'e lactam orif desired the lactam can be'rnixed into the nitropolymer' afterpolymerization. The pl asticizer is incorporated into the nitropolymerinamounts preferably from about 10% to about 40% by weight of thecomposition.

in addition, the lactams of this invention readily undergo heatpolymerization to produce polymers useful as ballistic modifiers forexplosives and combustible plastics. The polymers can be mixedwithconventional explosives such as PETN in any desired proportiondepending upon the oxygen balance desired. In addition, the polymerizedlactams of this invention afeus'eful intnemanuraetnre'dt shaped articlessuch as' are commonly produced fromther mosetting plastics.

The compounds of this invention are prepared by reacting a strongmineral acid salt of an" ester" of an amino acid with a moderatelystrong base, in-accordance with the general reaction scheme set forthbelow:

wherein R is an alkyl radical, Ais-a nitroalkylene-radical ticeof thisinvention are prepared by esterifying their ice acid. The amino acidsare obtained by hydrolysis of the corresponding nitrd-aza-aid halides,in accordance with the method disclosed in my cope'nding applicationSerial No. 426,902, filed April 30, 1954, now abandoned.

To more clearly illustrate invention, the rend examples are presented.It should be' understood; however, that these examples are presented merely as a means of illustration and are not messed to liiiiit the scopeof the invention iii an way.

' EXAMPLE I Preparation of 5,5 dinitr0hexan0lactam A flask provided witha stir'r'ei and thermometer was charged with 100 gm. methyl6-amino-4,4-dinitrohexanoate hydrochloride, 500 ml. water, and 1500 ml.ether. From a dropping funnel 230 of a 10% aqueousso' dium carbonatesolution was added gradually while s tir ring vigorously. Afterneutralization of all hydfochld'ric acid to a pH of 8, the ethersolution was separated, dried over sodium sulfate, and concentrated. Acolorless oil p was obtained, which did not crystallize. However, afterstanding overnight the oil was converted into white crys- These crystalswere triturated with methanol and crystallized from ethanol. The yieldwas 48 gm. and the MP. was 184-185 C. The elemental analysis of theproduct is as follows:

Calculated for CH N OI percent C, 35.47; percent H, 4.47; percent N,20.68; percent OCH;,, 0. Found: percent C, 35.58; percent H, 4.71;percent N, 22.17; percent OCH 0.

A wide variety of nitrd-snb'stitut'ed lactarns can be prepared inaccordance with the method described in Example I. For example,3,3-dinitrobutyrolactam is prepared from the acid salt of4-amino-2,2-dinitrobutanoic acid; 4,4-dinitrobutyrolactam is preparedfrom the acid salt of 4-amino-3,3-dinitrobutanoic acid;3',3'-difiitro'fifi tano'lactam is prepared from the acid salt ofS-amino- 2,2-dinitropentanoic acid; 4,4-dinitropentanolactam is preparedfrom the acid salt of 5-amino-3,3-dinitropentanoic acid;3,3-dinitropentanola'ctam is prepared from the acid salt of S-arnino2,2-diriitropentanoic acid; 5,5-dinitrohexanolactam is prepared from theacid salt, of 6-a'rriino 4,4 dinitrohxanoic' acid; 3,3-'dinitroliexanol; tam is prepared from the" acid salt ofG-aminO-AZ-dinitro hexanoic acid; 4,4-dinitrohexanolactarn is preparedfrom a the acid salt of 6-amino-3,3-dinitrohexanoic acid; 3,3,5,5-

tetranitropentanolactam is prepared from the acid salt of5-amino-2,2,4,4-tetranitropentanoic acid; 5,5-dinitrodecanolactam isprepared from the acid salt of 9-amino-4,4-d'initrononanoic acid; and4,4*-dinitrononalactarn is prepared from the acid salt of8-amino-3,3-dinitrooctanoic acid, by

proceeding in accordance with the examples and discussion set forthabove. Other members ofthis new clasd of corresponding aminoacids'tli'epr'esence of a mineral lactams can be prepared-ina' like manner.-

Any hydroxide or carbonate of an alkali or alkaline earth metal can beused to neutralize the mineral acid amine salt, however, sodiumcarbonate is preferred for reasons of cost, availability and its highsolubility. Hydrochloric acid salts arepreferred as a matter ofconvenience and availability.

This application is a coiitinuation-in-part of my copending applicationSerial No. 426,903, filed April 30, 1954, now abandoned.

1. As new compositi'oii's o f matter, thi nitio 's ubsfitu'tdii" lactamshaving the general formula A Nn ,, wherein A is a nitroalkyl ene radicalhaving at least three carbon atoms. 7

2. Asnew compositions o'f matter, the nitro-substituted lactams havingthe general formula wherein m and n are small whole numbers from to 4inclusive, provided that the sum of m plus n is greater than 1. -3. As anew composition of matter, 5,5-dinitrohexanolactam having the structuralformula H9? CHI 320 CH;

4. As a new composition of matter, 3,3-dinitrobutyrolactam having thestructural formula 5. As a new composition of matter,5,5-dinitrononalactam having the structural formula 6. As a newcomposition of matter, 4,4-dinitrobutyrolactam having the structuralformula 7. As a new compdsition of matter, 5,5-dinitropentanolactamhaving the structural formula 8. As a new composition of matter,4,4-dinitropentanolactam having the structural formula 9. As a newcomposition of matter, 3,3-dinitropentanolactam having the structuralformula 10. As a new composition of matter, 6,6-dinitrohexanolactamhaving the structural formula O:N NO: Ha H:

O=C-CH:

11. As a new composition of matter, 4,4-dinitrohexanolactam having thestructural formula 12. As a new composition of matter,3,3-dinitrohexanolactam having the structural formula 13. As a newcomposition of matter,3,3,5,$-tetranitropentanolactam having thestructural formula 14. The method of preparing nitro-lactams having thegeneral formula:

which comprises reacting a moderately strong base with a mineral acidsalt of an amino acid ester having the genwherein R is an alkyl radicaland m and n are whole numbers from 0 to 4 inclusive, provided the sum ofm plus n is greater than 1.

16. The method of claim 15 wherein said base is selected from the groupconsisting of alkali and alkaline earth metal carbonates and hydroxides.

17. The method of preparing 5,5-dinitrohexanolactam which comprisesreacting sodium carbonate and methyl 6-,amino-4,4-dinitrohexanoatehydrochloride.

No references cited.

1. AS NEW COMPOSITIONS OF MATTER, THE NITRO-SUBSTITUTED LACTAMS HAVINGTHE GENERAL FORMULA
 15. THE METHOD OF PREPARING NITRO-LACTAMS HAVING THEGENERAL FORMULA: